Disazo dyestuffs and their manufacture



Patented Nov. 26, 1940 DISAZO DYESTUFFS AND THEIR MANUF ACTURE Adolf Krebser, Riehen, near Basel, Switzerland, assignor to the firm J. R. Geigy, A. G., Basel,

Switzerland No Drawing. Application July 15, 1939, Serial No. 284,740. In Switzerland July 19, 1938 12 Claims.

The U. S. patent application Ser. No. 207,149, filed May 10, 1938, describes valuable red-violet to red-blue disazo-dyestuils based on the following general formula:

SOaH HO The U. S. patent application Ser. No. 257,721, filed February 21, 1939, refers to similar, violet to violet-blue disazo-dyestuffs of the following general formula:

NH: S 0311 OzY HO S OzZ HO wherein A means an aromatic radical of the benzene series, R means the radical of a phenol coupled in p-position, X represents hydrogen or an alkyl group, V represents hydrogen or a sulphonic acid group, X being hydrogen if V consists of a sulphonic acid group, and Z represents an aromatic radical of the benzene series containing a sulphonic acid group, such as a N- monoalkylated phenylamide group or a phenyl radical, also possess valuable properties and are similar to the dyestuffs cited in the aforesaid applications. By the introduction of a sulphonic acid group into the sulpho-N-alkylphenylamide group or into the phenylsulphone group it is for example possible to produce with -aoid and its monoalkyl derivatives still Well soluble dyestuffs. The new dyestuffs give in dyeing or printing in general navy-blue to green-blue shades and have very good fastness properties. Their manufacture is performed according to the different processes indicated in the aforesaid applications, by using the sulphonic acids of nitro-aminodiphenylsulphones or nitroaminobenzenesulphalkylarylides. The following examples illustrate the invention, the parts being by weight:

Example 1 35.8 parts of 5-nitro-2-amino-1:l-diphenylsulphone-3'-sulphonic acid are diazotised in aqueous solution according to known methods and coupled with 25.3 parts of 2-methylamino-8- naphthol-G-sulphonic acid in weakly mineralor acetic acid solution. After the formation of the dyestuff is achieved, the mass is rendered neutral 20 by means of sodium carbonate, the clear solution is heated to 55 C. and the nitro group is reduced by means of 11.7 parts of sodium sulphide of 100% strength. The aminomon'oazo-dyestufr is thereupon diazotised with 6.5 parts of nitrite and parts of hydrochloric acid of 30% strength at 0 C. and combined with a sodaalkaline solution of 9.5 parts of phenol. The combination is achieved within a short time. The mass is heated to 75 C., treated with sodium carbonate in excess, than with 40 parts ofp-toluenesulphonic acid chloride and kept at this temperature until the esterification is complete. Then it is salted out, filtered and dried. The new dyestuff, which constitutes a blue powder, is soluble in hot water with green-blue and in concentrated sulphuric acid with blue. coloration and dyes wool and silk from acid bath beautiful blue-green shades fast to light.

If instead of phenol m-cresol, 1:3:6-xyleno1 or other in p-position coupling substitution products of the phenol and instead of p-toluenesulphonic acid chloride other arylsulphonic acid chlorides, such as benzeneor p-chlorobenzenesulphonic acid chloride etc, are used, similar dyestuffs: will be obtained.

Instead of 2-methylamino-8-naphthol-6-sulphonic acid the 2-ethylor hydroxyethylamino- 8-naphtho1-6-sulphonic acid may be used with the same result. Instead of 5-nitro-2-amino- 1: 1-diphenylsu1phone-3'-sulphonic acid there may also be used the corresponding 5-nitro-2- amino-liY-phenyl-tolyl (or m-xy1yl-) sulphone- 3'-sulphonic acid. The production of these latter two compounds can be performed in a similar manner to that of the diphenlysulphone mentioned in the above example.

Example 2 rapidly 40 parts of sodium carbonate. When the coupling is achieved, the whole is heated to 75 C. and esterification is performed by means of 45 parts of p-toluenesulphonic acid chloride. By

salting out, filtration and drying a blue powder is obtained which dissolves in water with blue and in concentrated sulphuric acid with green-blue coloration and dyes wool and silk fast, reddishblueshades.

' A similar dyestuff is obtained if instead of the 5-nitro 2- amino-1:l'ediphenylsulphone-3-sulphonic acid 40.1 parts of 4-nitro-1-amino-2- sulphethylor -methyl-anilide -3'sulphonic acid is used. This compoundmay for examplebe prepared by causing 5-nitro-2-chlorobenzene sulphonic acid chloride to react with monoethylmetanilic acid and replacing the halogen by the amino group in the autoclave. Likewise the 2- sulphomethylor -ethyl-o-, -mor -p-toluiidide compounds are usable. Similar or analogous dyestuffs are obtained by the variations cited in 7 Example 1.

p Example 3 4.0.1 parts of -e-nitro-1-amino2-sulphethylanilide-3'-sulphonic acid are diazotised in aqueous solution and coupled in acid solution with 23.9 parts of 2-amino-8-naphthol-6 -sulphonic acid. After reduction of the nitro-monoazodyestuff by means of sodium sulphideat 50 C... the mass is diazotised with 6.5 parts of nitrite and 40 parts of hydrochloric acid of 30% strength and combined to the disazo-dyestuff with 9.5 parts of phenol in sodaalkaline solution. After short time the coupling is achieved, the whole is heated to 75 C. andesterification is performed by means of 45 parts of p-toluenesulphom'c acid chloride. The dyestuff solution is rendered weakly acid and salted out. The new dye-stuff, a blue powder, is soluble in water with blue-violet and in concentrated sulphuric acid with blue coloration and dyes wool and silk beautiful, navy-blue shades.

By variation of the diazo-, phenolor aryl-sulphonic acid chloride components, such as they are for example given in the Examples 1 and 2, disaz odyestuifs with similar properties can be produced.

With respect to-the preparation of the starting material,.201 parts of ethylmetanilic acid are treated in presence of an excess of acetate in aqueous solution at 75v C. with 305 parts of 5-nitro-2- chlorobenzenesulphochloride. After the reaction is achieved, the 4-nitro-l-chloro-Z-sulphethylanilide-3'-sulphonic acid is precipitated by means of potassium chloride and filtered. Thereupon the chlorine is exchanged in the autoclave with ammonia in excess at 160 C. The obtained potassium salt of the 4-nitro-1-amino-2-sulphethylanilide-3-su1phonic acid is easily soluble in hot water, more difiicultly soluble in cold water. It crystallises out in form of thin pale-greenish 7 leaves.

What I claim is: 1. Disazo-dyestufis of the formula wherein A means an aromatic radical of the benzene series, B the radical of a phenol coupled in p-position, X means a member of the group consisting of hydrogen and alkyl, V means a member of the group consisting of hydrogen and a sulphonic acid group (X being hydrogen if V is a sulphonic acid group) and Z represents a radical of the group consisting of an aminophenyl-sulphonic acid radical connected through 20 the-amino group with the SOz-group and a phenylsulphonic acid radical connected through a nuclear carbon atom with the SOz-group.

2. Disazo-dyestuffs of the formula I S OnZ HO I S OaH wherein A means an aromatic radical of the benzene series, R the radical of a phenol coupled in p-position, X means a member of the group consisting of hydrogen and alkyl, V means amember of the group consisting of hydrogen and a sulphonic acid group (X being hydrogen if V is a sulphonic acid group) and Z represents a phenyl radical containing a sulphonic acid group.

4. A process for the manufacture of disazodyestuffs, which comprises combining a diazotised monoazo-dyestuff of the formula wherein R representsthe radical of a phenol coupledin p-pos it ion and Z represents a radical of 70 the group consisting of an amino-phenyl-sulphonic acid radical connected through the amino group with the Son-group and a phenylsulphonic acid radical connected through a nuclear carbon atom with the S02-group, in acid solution with a 2:B-aminonaphtholsulphonic acid of the formula wherein X represents a member of the group consisting of hydrogen and alkyl and V represents a member of the group consisting of hydrogen and a sulphonic acid group (X being hydrogen if V is a sulphonic acid group), and after-treating the obtained disazo-dyestuff with a halogenide of a sulphonic acid of the benzene series.

5. A process for the manufacture of disazodyestuifs, which comprises combining a diazotised monoazo-dyestuff of the formula wherein R represents the radical of a phenol coupled in p-position and Z represents a radical of the group consisting of an amino-phenyl-sulphonic acid radical connected through the amino group with the SOz-group and a phenylsulphonic acid radical connected through a nuclear carbon atom with the SOs-group, in acid solution with a 2:8-aminonaphtholsulphonic acid of the formula 60 wherein X represents a member of the group consisting of hydrogen and alkyl, V represents a member of the group consisting of hydrogen and sulphonic acid group (X being hydrogen when V represents a sulphonic acid group), Z represents 65 a radical of the group consisting of an aminophenyl-sulphonic acid radical connected through the amino group with the SOz-group and a phenylsulphonie acid radical connected through a nuclear carbon atom with the SOi-group, and

70 then converting said intermediate by diazotizing HO.R.N=NON=N l S OzZ HO OsH wherein X, V and Z have the meanings above set forth, and R represents the radical of a phenol coupled in p-position, and after-treating the obtained disazodyestuff with an arylsulphonic acid chloride of the benzene series.

7. A process for the manufacture of a disazodyestuif, which comprises coupling diazotised 5- nitro 2 amino-1:1-diphenylsulphone 3-sulphonic acid with 2-methy1amino-8-naphthol-6- sulphonic acid, reducing the nitro group, diazotising the aminomonoazodyestuff thus obtained, coupling with phenol and reacting with p-toluenesulphonic acid chloride.

8. A process for the manufacture of a disazodyestuff, which comprises coupling diazotized 5- nitro 2 amino-1:1-pheny1-tolyl-sulphone-3- sulphonic acid with Z-ethylamino-8-naphthol-6- sulphonic acid, reducing the nitro group, diazotising the aminomonoazodyestuff thus obtained, coupling with phenol and reacting with p-tcluene-sulphonic acid chloride. I

9. A process for the manufacture of a disazodyestuff, which comprises coupling diazotised 5- nitro 2 amino-1:1-diphenylsulphone-3-sulphonic acid with 2-amino-8-naphthol 3:G-disulphonic acid, reducing the nitro group, diazotising the aminomonoazodyestuff thus obtained, coupling with m-cresol and reacting with p-toluenesulphonic acid chloride.

10. The disazo-dyestufi having the formula NHCHs CHaO-SOz.O-ON=N -N=N on son;

SOIH 11. The disazo-dyestuflf having the formula NJELOH: om-OsmoOmN N=N H0 OaH somirQ CzHs 801B 12. The disazo-dyestuif having the formula NHa/SOzH orn-OsomO =N N=N soan ADOLF IKREBSER. 

